WO2000018897A1 - Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose - Google Patents

Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose Download PDF

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Publication number
WO2000018897A1
WO2000018897A1 PCT/US1998/020491 US9820491W WO0018897A1 WO 2000018897 A1 WO2000018897 A1 WO 2000018897A1 US 9820491 W US9820491 W US 9820491W WO 0018897 A1 WO0018897 A1 WO 0018897A1
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WO
WIPO (PCT)
Prior art keywords
cbd
fabric
chemical
chemical entity
entity according
Prior art date
Application number
PCT/US1998/020491
Other languages
English (en)
Inventor
Johan Smets
Jean-Luc Phlippe Bettiol
Christophe Laudamiel
Stanton Lane Boyer
Andre Cesar Baeck
Ivan Maurice Alfons Jan Herbots
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The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22267976&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000018897(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP98949649A priority Critical patent/EP1119613A1/fr
Priority to MXPA01003381 priority patent/MXPA01003381A/es
Priority to BR9816038-9A priority patent/BR9816038A/pt
Priority to CA002343267A priority patent/CA2343267A1/fr
Priority to PCT/US1998/020491 priority patent/WO2000018897A1/fr
Priority to AU95930/98A priority patent/AU9593098A/en
Priority to JP2000572344A priority patent/JP2002525423A/ja
Priority to CN98814341A priority patent/CN1327478A/zh
Priority to PCT/US1999/010854 priority patent/WO2000018865A1/fr
Priority to CN99813900A priority patent/CN1329658A/zh
Priority to ES99923145T priority patent/ES2263273T3/es
Priority to EP99923146A priority patent/EP1117757A1/fr
Priority to CA002342588A priority patent/CA2342588A1/fr
Priority to CA002342586A priority patent/CA2342586A1/fr
Priority to CA002342530A priority patent/CA2342530A1/fr
Priority to AU39982/99A priority patent/AU3998299A/en
Priority to CN99813903A priority patent/CN1329659A/zh
Priority to DE69930858T priority patent/DE69930858T2/de
Priority to AT99923145T priority patent/ATE323146T1/de
Priority to BR9914110-8A priority patent/BR9914110A/pt
Priority to AU39981/99A priority patent/AU3998199A/en
Priority to BR9914182-5A priority patent/BR9914182A/pt
Priority to PCT/US1999/010853 priority patent/WO2000018864A1/fr
Priority to CN99813904A priority patent/CN1329666A/zh
Priority to PCT/US1999/010855 priority patent/WO2000018898A1/fr
Priority to EP99924286A priority patent/EP1117770A1/fr
Priority to JP2000572313A priority patent/JP2003521558A/ja
Priority to EP99923145A priority patent/EP1115828B1/fr
Priority to JP2000572312A priority patent/JP2003526699A/ja
Priority to JP2000572345A priority patent/JP2003521559A/ja
Priority to AU40823/99A priority patent/AU4082399A/en
Priority to ARP990104946A priority patent/AR020546A1/es
Priority to ARP990104944A priority patent/AR020544A1/es
Priority to ARP990104945A priority patent/AR020545A1/es
Priority to ARP990104943A priority patent/AR020543A1/es
Publication of WO2000018897A1 publication Critical patent/WO2000018897A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405—Glucanases
    • C12N9/2434—Glucanases acting on beta-1,4-glucosidic bonds
    • C12N9/2437—Cellulases (3.2.1.4; 3.2.1.74; 3.2.1.91; 3.2.1.150)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
    • C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
    • C12N9/52—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea
    • C12N9/54—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea bacteria being Bacillus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/195—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from bacteria
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/195—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from bacteria
    • C07K14/32—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from bacteria from Bacillus (G)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/195—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from bacteria
    • C07K14/33—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from bacteria from Clostridium (G)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/37—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from fungi
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004—Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the present invention relates to a chemical entity comprising more than one chemical components linked to a Cellulose Binding Domain (CBD).
  • CBD Cellulose Binding Domain
  • Modern laundry detergent and/or fabric care compositions contain various detergent ingredients having one or more purposes in obtaining fabrics which are not only clean, fresh and sanitised but also have retained appearance and integrity. Therefore, detergent components such as perfumes, soil release agents, fabric brightening agents, fabric softeners, chelants, bleaching agents and catalysts, dye fixatives and enzymes, have been incorporated in laundry detergent and/or fabric care compositions. In using such detergent components, it is important that some of these compounds deposit on the fabrics so as to be effective during or after the laundering and/or fabric care process.
  • cellulase enzymes for the treatment of cotton- containing fabrics which largely consist of cellulose.
  • the cellulose structures are depolymerized or cleaved by cellulases into smaller and thereby more soluble or dispersible fractions.
  • This activity in particular on fabrics provides a cleaning, rejuvenation, softening and generally improved handfeel characteristics to the fabric structure.
  • cellulase enzymes it has been difficult to incorporate cellulase enzymes into modern detergents in an effective manner.
  • those skilled in the art have sought to use minimal amounts of cellulase to their fullest effectiveness by ensuring that most, if not all, of the cellulase enzyme comprised in the detergent composition deposits on the fabric.
  • optimum cellulases would generally have a binding domain especially suitable for celluloses. In this way, most of the cellulase enzyme included in the detergent composition deposits or otherwise binds to the fabric during the laundering cycle to achieve its desired results.
  • laundry detergent and/or fabric care compositions in which chemical components are also modified to ensure deposition onto the fabrics for improved and/or new performances.
  • laundry detergent and/or fabric care compositions comprising a chemical entity comprising more than one chemical components linked to a cellulose binding domain. It has been surprisingly found that such chemical entities more readily affix or otherwise come into contact with the fabric, thereby resulting in new, increased, enhanced and/or more cost-effective performance of the chemical component at the fabric surface or when released during or after the laundry and/or fabric care process.
  • WO 91/10732 describes novel derivatives of cellulase enzymes combining a core region derived from an endoglucanase producible by a strain of Bacillus spp., NICMB 40250 with a CBD derived from another cellulase enzyme, or combining a core region derived from another cellulase enzyme with a CBD derived from said endoglucanase, for improved binding properties.
  • WO94/07998 describes cellulase variants of a cellulase classified in family 45, comprising a CBD, a Catalytically Active Domain (CAD) and a region linking the CBD to the CAD, wherein one or more amino acid residues have been added, deleted or substituted and /or another CBD is added at the opposite end of the CAD.
  • WO95/16782 relates to the cloning and high level expression of novel truncated cellulase proteins or derivatives thereof in Trichoderma longibrachiatum comprising different core regions with several CBDs.
  • WO97/01629 describes cellulolytic enzyme preparation wherein the mobility of the cellulase component may be reduced by adsorption to an insoluble or soluble carrier e.g. via the existing or newly introduced CBD.
  • WO97/28243 describes a process for removal or bleaching or soiling or stains from cellulosic fabrics wherein the fabric is contacted in aqueous medium with a modified enzyme which comprises a catalytically active amino acid sequence of a non-cellulolytic enzyme selected from amylases, proteases, lipases, pectinases and oxidoreductases, linked to an amino acid sequence comprising a cellulose binding domain and a detergent composition comprising such modified enzyme and a surfactant.
  • WO98/00500 discloses a composition comprising a protein deposition aid having a high affinity for fibres or a surface and having a benefit agent attached / adsorbed thereto.
  • the present invention relates to a chemical entity comprising more than one chemical components linked to an amino acid sequence comprising a Cellulose Binding Domain.
  • the present invention further relates to laundry detergent and/or fabric care compositions comprising one or more of such chemical entities. These compositions provide new, increased, enhanced and/or more cost-effective performance of the chemical components.
  • the present invention also relates to a method of treating a fabric with a chemical entity, comprising the steps of :
  • the present invention further relates to the use of a cellulose binding domain to deposit a chemical component onto a fabric wherein the chemical component is attached to the cellulose binding domain.
  • the present invention finally relates to a process for attaching a chemical component to a cellulose binding domain comprising the steps of in any order : (i) reacting the chemical components to the linking region; and/or (ii) reacting the linking region with the cellulose binding domain.
  • the object of the present invention is to increase and/or enhance the performance and cost effectiveness of chemical components.
  • This object is achieved by the formulation of a chemical entity which comprise more than one chemical components linked to an amino acid sequence comprising a cellulose binding domain. It has been surprisingly found that such chemical entities more readily affix or otherwise come into contact with the fabric, thereby resulting in new, increased and/or enhanced performance of the chemical component at the fabric surface or when released during or after the laundry and/or fabric care process. Accordingly, this allows to formulate compositions in a more cost- effective manner.
  • the present invention relates to a chemical entity having a ratio of chemical components to Cellulose Binding Domain unit (CBD) higher than 1. This can be achieved by :
  • - The linking of all chemical components directly to a selected cellulose binding domain.
  • Said cellulose binding domain is selected to comprise in its amino acid sequence, at least one Lysine amino acid. Lysine amino acid(s) and the terminal amino acid will provide suitable attachment points for chemical components.
  • - The linking of at least one chemical component directly to the cellulose binding domain and at least one chemical component indirectly to said cellulose binding domain via a linking region. In this instance, at least one chemical will be attached to the reactive group of an amino acid comprised in the sequence of the cellulose binding domain. At least another chemical component will be linked to said CBD via a linking region.
  • polyreactive linking region The linking of all chemical components indirectly to a cellulose binding domain via a linking region comprising more than one reactive site suitable for the linking of a chemical component, hereinafter referred to as "polyreactive linking region".
  • amino acid sequence comprising a cellulose binding domain comprises at least one Lysine amino acid.
  • the present invention further encompasses chemical entities wherein the chemical component is linked to the CBD, linking region and/or polyreactive linking region by a weak bond.
  • Said weak bonds are cleaved during or after the wash or fabric care process, allowing the release of the attached chemical component(s).
  • the perfume component, insect control agent, hygiene agent will be linked via a weak bond.
  • Identical or different chemical components can be linked to a CBD.
  • the chemical components encompassed in the present invention are preferably selected from the group consisting of perfumes, hygiene agents, insect control agent, softener compounds, soil release polymers, bleaching agents, dye fixatives agents, brighteners and/or mixtures thereof. More preferred components are the perfume components, insect control agents, hygiene agents and/or bleaching agents.
  • compositions of the present invention can comprise the same chemical components unmodified.
  • linking region is intended to indicate a region that adjoins the CBD and connects it to the chemical components.
  • the linking region is an intermediate between the chemical components and the amino acid sequence comprising a cellulose binding domain. This linking region comprises a moiety that will covalently bind to the CBD and one or more reactive group available to attach a chemical component.
  • linking regions characterised by having at least one attachment point for a chemical component and at least one attachment point to the cellulose binding domain.
  • the linking regions of the present invention will encompass at least one attachment point to the cellulose binding domain and more than one reactive group available to attach a chemical component, hereinafter referred to as "polyreactive linking region”.
  • Suitable linking regions are :
  • polyethylene glycol derivatives described in the Shearwater polymers, Inc. catalogue of January 1996 such as the nucleophilic PEGs, the carboxyl PEGs, the electrophilically activated PEGs, the sulfhydryl-selective PEGs, the heterofunctional PEGs, the biotin PEGs, the vinyl derivatives, the PEG silanes and the PEG phospholipids.
  • Particularly suitable specifically substituted polymers are the heterofunctional PEG, (X-PEG-Y) polymers from Shearwater such as PEG(NPC)2, PEG-(NH2)2, t-BOC-NH-PEG-NH2, t-BOC-NH-PEG-CO2NHS, OH- PEG-NH-tBOC, FMOC-NH-PEG-CO2NHS or PEG(NPC)2 MW 3400 from Sigma.
  • Preferred polymers are PEG(NPC)2, (NH2)2-PEG, t-BOC-NH-PEG-NH2 polymers, more preferred is t-BOC-NH-PEG-NH2 polymer from Shearwater.
  • DSS disuccinimidyl suberate
  • GMBS ⁇ -maleimidobutyric acid N-hydroxysuccinimide ester
  • EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride
  • DMS dimethyl suberimidate hydrochloride
  • Suitable linking regions, in particular polyreactive linking regions include the polyacrylic acid/ maleic acid polymer, polyvinyl alcohol polymer, amino-containing compounds and/or mixtures thereof such as described below.
  • the amine- containing compounds include the amino aryl derivatives, the polyamines, the substituted amines and amides, the glucamines, the dendrimers / chitosan saccharides and amine derivatives polysaccharides and the peptidic polymers.
  • Poly vinyl alcohol polymers These polymers can still comprise or not the moiety containing the polymerisation initiator. - Without the acid moiety containing initiator of polymerisation, this polymer can be linked for example, to the reactive group of aspartic or glutamic acid present in the amino acid sequence of the CBD via an esterification reaction.
  • the poly vinyl alcohol polymer does further comprise hydroxyl reactive groups available for attachment of acid/aldehyde containing chemical components.
  • this acid moiety of the initiator of polymerisation of the polymer for example, can be linked for example, to a NH2 group present in the amino acid CBD sequence.
  • the poly vinyl alcohol polymer does further comprise hydroxyl reactive groups available for attachment of acid/aldehyde containing chemical components.
  • amine-containing compounds having the following general structure : B-(NH2) n ; wherein B is a carrier material, and n is an index of value of at least 1.
  • B carriers are inorganic or organic carriers.
  • inorganic carrier carrier which are non- or substantially non carbon based backbones.
  • preferred inorganic carriers are mono or polymers or organic-organosilicon copolymers of amino derivatised organo silane, siloxane, silazane, alumane, aluminum siloxane, or aluminum silicate compounds.
  • Typical examples of such carriers are: organosiloxanes with at least one primary amine moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5) 3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll, Academic Press Inc. 1998, London, pp 209, 106).
  • Mono or polymer or organic-organosilicon copolymers containing one or more organosilylhydrasine moiety are also preferred.
  • a typical example of such a class of carrier material is the N,N'-bis(trimethylsilyl)hydrazine (Me3Si) 2NNH2 described in: The OrganoSilicon Chemistry Second international Symposium, Pure and Applied Chemistry, Vol, 19 Nos 3-4, (1969).
  • polymer silicone derivatives are the cyclic 1 ,1 ,5,5,7,7,711 ,11-Octamethyl-3-9-bis-[2-(2- aminoethylamino)-ethyl]-1 ,5,7,11-tetrasila-3,9-diaza-6,12-dioxacyclododecane and the Hexaethoxydiamino cyclotetrasiloxane (C6H5) (NH2) 2Si4O4, id, Vol 2 part 2, p 474, p454).
  • Preferred amino functionalized inorganic polymeric carriers for use herein are polyaminoalkyl polysiloxanes.
  • inorganic polymeric carriers suitable for use herein are the amino functionalized polydi-alkylsiloxanes, as described in EP 150 867 and having the general formula:
  • R C,. 16 preferentially C ⁇ alkyl
  • n is an integer from 0 to 16 preferentially from 1 to 6
  • organic carriers By organic carriers, it meant carriers having essentially carbon bond backbones.
  • Typical amines having organic carrier include aminoaryl derivatives, polyamines, aminofunctional polymers, aminoacids and derivatives, substituted mono-, oligo- and poly amino saccharides, substituted amines and amides, dendrimers, and glucamines.
  • amine compound can be interrupted or substituted by linkers or cellulose substantive group.
  • a general formula for this amine compound may be represented as follows:
  • each m is an index of value 0 or at least 1
  • n is an index of value of at least 1 as defined herein before.
  • the amine group is linked to a carrier molecule as defined by classes hereinafter described.
  • the primary amine group is either directly linked to the carrier group or via a linker group L.
  • the carrier can also be substituted by a R * substituent, and R * can be linked to the carrier either directly or via a linker group L.
  • R* can also contain branching groups like e.g. tertiary amine and amide groups.
  • the amine compound comprises at least one primary amine group to react with a chemical component of the present invention to form the reaction products.
  • the amine compound is not limited to having only one amine function. Indeed, more preferably, the amine compound comprises more than one amine function, thereby enabling the amine compound to react with several chemical components of the present invention.
  • reaction products carrying mixed perfumes aldehyde(s) and/or ketone(s) can be achieved, thereby resulting in a mixed release of such fragrances.
  • Typical linker group include:
  • L can also contain — o — if this group is not directly linked to N
  • R * contains 1 to 22 carbon atoms in the main chain and optionally can be an alkyl, alkenyl, or alkylbenzene chain. It can also contain alicyclic, aromatic, heteroaromatic or heterocyclic systems, either inserted into the main chain or by substitution of an H atom of the main chain. Further, R * can either be linked to the carrier B material or via a linker L, as defined herein before. In this instance, L can also be -O-.
  • the main chain can contain from 1 to up to 15 R * groups.
  • Typical R * insertion groups include:
  • R* can also contain several insertion groups linked together: e.g. eg- — -CH 2 -CH 2 -O-CH 2 -CH 2 -O-C-
  • R* can carry a functional end group E that provides additional surface substantivity.
  • Typical organic groups of this end group E include o
  • E can also be an aromatic, alicyclic, heteroaromatic, or heterocyclic group including mono-, oligo-, polysaccharides
  • R* group can also be modified via substitution of one or more H atoms in the main chain.
  • the substitution group can either be E or the insertion groups as defined above where the insertion group is terminated by any of H, E, or R * .
  • R * can also be a group made of ethoxy or epoxy groups with n ranging from 1 to 15, including groups like:
  • preferred amine having organic carrier material B may be selected from aminoaryl derivatives, polyamines, aminoacids and derivatives, substituted amines and amides, and glucamines.
  • the amino group is preferably attached to a benzene ring.
  • the benzene ring is further substituted in the para- and/or meta-position with R * as defined herein before.
  • R* can be attached to the benzene ring via a linker L.
  • the benzene ring can be substituted by other aromatic ring systems including naphtalene, indole, benzimidazole, pyrimidine, purine, and mixtures thereof.
  • the R * is attached to the benzene ring in its para position.
  • Typical amino-benzene derivatives have the following formula:
  • Preferred amino-benzene derivatives have the following formula:
  • Preferred amino-benzene derivatives are alkyl esters of 4-amino benzoate compounds, preferably selected from ethyl-4-amino benzoate, phenylethyl-4- aminobenzoate, phenyl-4-aminobenzoate, 4-amino-N'-(3-aminopropyl)- benzamide, and mixtures thereof.
  • the polyamines of the invention need to have at least one, preferably more than one free and unmodified primary amine group, to react with a chemical component of the present invention.
  • H can be substituted by R*, optionally via a linker group L.
  • the primary amine group can be linked to the polymer end via a linker group L.
  • the polyamines compounds suitable for use in the present invention are water- soluble or dispersible, polyamines.
  • the amino-functional polymers for use herein have a molecular weight between 150 and 2 * 10 6 , preferably between 400 and 10 6 , most preferably between 5000 and 10 6 .
  • These polyamines comprise backbones that can be either linear or cyclic.
  • the polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
  • the polyamine backbones described herein are modified in such a manner that at least one, preferably each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
  • the term "modification" as it relates to the chemical structure of the polyamines is defined as replacing a backbone -NH hydrogen atom by an R' unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide (oxidised).
  • substitution and “substitution” are used interchangeably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an R' unit. Quaternization or oxidation may take place in some circumstances without substitution, but substitution is preferably accompanied by oxidation or quaternization of at least one backbone nitrogen.
  • linear or non-cyclic polyamine backbones that comprise the amino-functional polymer have the general formula:
  • primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units.
  • V or Z "terminal" units when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure
  • H2N-[R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
  • V terminal
  • some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain “terminal” units.
  • Z Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
  • secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units.
  • W backbone
  • — ⁇ N-R]— is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit.
  • W backbone
  • some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain “backbone” units.
  • tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
  • Y branch point of either the polyamine backbone or other branching chains or rings, having the structure
  • V(n+1)WmYnZ for linear amino-functional polymer and by the general formula V(n-k+1)WmYnY'kZ for cyclic amino-functional polymer.
  • [N-R]— serves as a branch point for a backbone or branch ring.
  • Y' unit there is a Y unit having the formula
  • the polyamine backbone has the formula
  • the polyamine backbones of the present invention comprise no rings.
  • the ratio of the index n to the index m relates to the relative degree of branching.
  • a fully non-branched linear modified polyamine according to the present invention has the formula V /VmZ that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule.
  • the value for m ranges from a minimum value of 2 to 700, preferably 4 to 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred.
  • Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, Y' or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units or Y 1 units and unmodified tertiary amine nitrogens are Y units for the purposes of the present invention.
  • Modified primary amine moieties are defined as V "terminal" units having one of three forms: a) simple substituted units having the structure:
  • Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure:
  • R' b quaternized units having the structure:
  • modified secondary amine moieties are defined as Y' units having one of three forms: a) simple substituted units having the structure: -N-R-
  • Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure:
  • Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms: a) simple substituted units having the structure:
  • R' b quaternized units having the structure:
  • a primary amine unit comprising one R' unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH2CH2)HN-.
  • the Z "terminal” unit derives from a terminal primary amino moiety of the structure -NH2.
  • Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
  • the Z "terminal” unit can be substituted with any of the R' units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore R' cannot be a hydrogen.
  • the polyamines of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone.
  • R units comprise units that for the purposes of the present invention are referred to as “hydrocarbyl R” units and “oxy R” units.
  • the "hydrocarbyl” R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; C8-
  • C12 dialkylarylene which for the purpose of the present invention are arylene moieties having two alkyl substituent groups as part of the linking chain.
  • a dialkylarylene unit has the formula
  • the unit need not be 1 ,4-substituted, but can also be 1 ,2 or 1 ,3 substituted C2-C12 alkylene, preferably ethylene, 1 ,2-propylene, and mixtures thereof, more preferably ethylene.
  • the "oxy" R units comprise - (R1O)xR5(OR1)x-, -CH2CH(OR2)CH2O)z(R1O)yR1 (OCH2CH(OR2)CH2)w-, - CH2CH(OR2)CH2-, -(R1O)xR1-, and mixtures thereof.
  • R units are selected from the group consisting of C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -(R1O)xR1-, CH2CH(OR2)CH2-, -(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH-(OH)CH2)w-, - (R1O)xR5(OR1)x-, more preferred R units are C2-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12 dihydroxyalkylene, -(R1O)xR1-, -(R1O)xR5(OR1)x-, - (CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH-(OH)CH2)w-, and mixtures thereof, even more preferred R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixture
  • R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
  • R2 is hydrogen, and -(R1O)xB, preferably hydrogen.
  • R3 is C1-C18 alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-C12 aryl, and mixtures thereof , preferably C1-C12 alkyl, C7-C12 arylalkylene, more preferably C1-C12 alkyl, most preferably methyl.
  • R3 units serve as part of R' units described herein below.
  • R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, preferably C1-C10 alkylene, C8-C12 arylalkylene, more preferably C2-
  • C8 alkylene most preferably ethylene or butylene.
  • R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-
  • CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-, -C(O)(R4)rC(O)-, CH2CH(OH)CH2- R5 is preferably ethylene, -C(O)-, -C(O)NHR6NHC(O)-, -
  • R6 is C2-C12 alkylene or C6-C12 arylene.
  • the preferred "oxy" R units are further defined in terms of the R1 , R2, and R5 units.
  • Preferred "oxy" R units comprise the preferred R1 , R2, and R5 units.
  • the preferred polyamines of the present invention comprise at least 50% R1 units that are ethylene.
  • Preferred R1 , R2, and R5 units are combined with the "oxy" R units to yield the preferred "oxy” R units in the following manner.
  • R' units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3- C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -(CH2)pCO2M, - (CH2)qSO3M, -CH(CH2CO2M)CO2M, -(CH2)pPO3M, -(R1O)mB, -C(O)R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C1-C22 alkylene, - (R1O)mB, -C(O)R3, -(CH2)pCO2M, -(CH2)qSO3M, -CH(CH2CO2M)CO
  • R' units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides.
  • the backbone chain or branching chains do not comprise units of the following structure:
  • R' units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N- oxides.
  • the R' unit -C(O)R3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure or combinations thereof.
  • B is hydrogen, C1-C6 alkyl, -(CH2)qSO3M, -(CH2)pCO2M, -(CH2)q- (CHSO3M)CH2SO3M, -(CH2)q(CHSO2M)CH2SO3M, -(CH2)pPO3M, -PO3M, preferably hydrogen, -(CH2)qSO3M, -(CH2)q(CHSO3M)CH2SO3M, -(CH2)q- (CHSO2M)CH2SO3M, more preferably hydrogen or -(CH2)qSO3M.
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
  • a sodium cation equally satisfies -(CH2)pCO2M, and -(CH2)qSO3M, thereby resulting in -(CH2)pCO2Na, and -(CH2)qSO3Na moieties.
  • More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
  • more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical.
  • a -(CH2)pPO3M moiety substituted with sodium atoms has the formula -(CH2)pPO3Na3.
  • Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may be substituted for or combined with other suitable mono-valent water soluble cations.
  • Preferred cations are sodium and potassium, more preferred is sodium.
  • X is a water soluble anion such as chlorine (CI-), bromine (Br-) and iodine
  • (I-) or X can be any negatively charged radical such as sulfate (SO42-) and methosulfate (CH3SO3-).
  • indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1 ; w has the value 0 or 1 , x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1 ; m has the value from 2 to 700, preferably from 4 to 400, n has the value from 0 to 350, preferably from 0 to 200; m + n has the value of at least 5.
  • x has a value lying in the range of from 1 to 20, preferably from 1 to 10.
  • the preferred amino-functional polymers of the present invention comprise polyamine backbones wherein less than 50% of the R groups comprise "oxy" R units, preferably less than 20% , more preferably less than 5%, most preferably the R units comprise no "oxy" R units.
  • the most preferred amino-functional polymers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms.
  • ethylene, 1 ,2-propylene, and 1 ,3- propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
  • the amino-functional polymers of the present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified.
  • the term "homogeneous polyamine backbone” is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artefact of the chosen method of chemical synthesis.
  • ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator” would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
  • a polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone.
  • a polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless of the degree of branching or the number of cyclic branches present.
  • non-homogeneous polymer backbone refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
  • a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1 ,2-propylene units.
  • a mixture of "hydrocarbyl” and “oxy” R units is not necessary to provide a non-homogeneous backbone.
  • Preferred amino-functional polymers of the present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
  • not all backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator.
  • the preferred polyamines that comprise the backbone of the compounds of the present invention are generally polyalkyleneimines (PAI's), preferably polyethyleneimines (PEI's), or PEI's connected by moieties having longer R units than the parent PAI's or PEI's.
  • PAI's polyalkyleneimines
  • PEI's polyethyleneimines
  • PEI's polyethyleneimines
  • Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethylenimines (PEI's).
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1 , however PEI's having a ratio of m to n of 2:1 are most preferred.
  • Preferred backbones, prior to modification have the general formula:
  • PEI's will have a molecular weight greater than 200 daltons.
  • the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
  • polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21 , 1951 ; all herein incorporated by reference.
  • Preferred polyamines are polyethyleneimines commercially available under the tradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P, PS, SK, SNA.
  • Still other polyamines suitable for use in the present invention are poly[oxy(methyl-1 ,2-ethanediyl)], ⁇ -(2-aminomethylethyl)- ⁇ -(2-aminomethyl- ethoxy)-; poly[oxy(methyl-1 ,2-ethanediyl)], ⁇ -hydro-)- ⁇ -(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1 ,3-propanediol; commercially available under the tradename Jeffamines T-403, D-230, D-400, D-2000; 2,2',2"- triaminotriethylamine; 2,2'-diamino-diethylamine; 3,3'-diamino-dipropylamine, 1 ,3 bis aminoethylcyclohexane commercially available from Mitsibushi and the C12 Sternamines commercially available from Clariant like the C12 Sternamin(propylen
  • Substituted amine and amide compounds suitable for use herein have the following general formula: NH2-L-R**, in which L is -CO- in case of an amide.
  • Other optional linker group may be as defined under R*.
  • R ** is as defined herein before under R * with the proviso that it contains at least 6 carbon atoms and/or N atoms and/or cyclohexyl-, piperidine, piperazine, and other heterocyclic groups like:
  • H in NH can be substituted by R*.
  • Preferred substituted amines and amides for use herein are selected from nipecotamide, N-coco-1 ,3-propenediamine; N-oleyl-1 ,3-propenediamine; N- (tallow alkyl)-1 ,3-propenediamine; 1 ,4-diamino cyclohexane; 1 ,2-diamino- cyclohexane; 1 ,12-diaminododecane, and mixtures thereof.
  • Still a further preferred class of amine compound is the class of glucamines of general structure: NH2-CH2-(CH(OH)) x -CH2OH, wherein one or several OH- function can be substituted, preferably by -OR * , and wherein x is an integer of value 3 or 4.
  • R * can be linked to the OH groups either directly or via linker unit as mentioned herein before under L.
  • Preferred compound of this class are selected from 2,3,4,5,6-pentamethoxy- glucamine; 6-acetylglucamine, glucamine, and mixture thereof.
  • chitosan saccharides amine derivatives polysaccharides are also suitable.
  • dendrimers such as Starburst or Astramol sold from DSM or Aldrich and the Oligo- or Poly-saccharides derivatised amines like chitosan and/or derivatives sold by Henkel or Amerchol and like the functionalised oligosaccharides and glycans, especially the Amine & other Nitrogen containing materials sold by Carbomer Inc.
  • Most preferred compounds for use in the present invention are amino acids and their derivatives, especially ester and amide derivatives. These peptidic polymers are linked to the CBD via a peptidic linkage. More preferred compounds are those providing enhanced surface substantivity due to its structural feature. Suitable amino acids have the following functionality of formula:
  • Suitable amino acids for use herein are selected tyrosine, tryptophane, lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine, phenylalanine, proline, glycine, serine, histidine, threonine, methionine, and mixture thereof.
  • Homopolymers with the same amino acids or heteropolymers with different amino acids are suitable.
  • the amino acids Serine, Threonine and Tyrosine possess the reactive hydroxyl group
  • the Cysteine present a reactive SH group
  • the Asparagine and Glutamine amino acids possess a reactive amido group and the Lysine a reactive amino group.
  • the linking will preferably be achieved on the Tyrosine, Cysteine or Lysine.
  • the free NH2 group from a Lysine amino acid or of the terminal amino acid within the peptidic polymer is used as attachment points for chemicals containing aldehyde, ene one, ketone, or acid or halogene moeities
  • amino acid derivatives selected from tyrosine ethylate, glycine methylate, tryptophane ethylate and mixture thereof,
  • peptidic polymers can be attached to the amino acid sequence comprising a cellulose binding domain, by recombinant technology.
  • An example of the recombinant technique describing the expression of an enzyme with the CBD of different origin is described in S. Karita et al., (1996) Journal of Fermentation and Bioengineering, Vol. 81 , No. 6, pp. 553-556.
  • the polyreactive linking region can comprise from 1 to about 100 amino acid residues, in particular of from 2 to 40 amino acid residues, e.g. from 2 to 15 amino acid residues. It is preferred to use amino acids which are less favoured by the surrounding proteases. Indeed, any combination of amino acids can be selected to achieve maximal weight efficiency and protease stability.
  • weak bond is a bond which can be enzymatically cleaved, oxidised, cleaved by light radiation and/or hydrolysed during or after the wash/fabric care process in order to release the chemical component(s).
  • weak bonds are Shiff-base or beta-amino-ketone linking.
  • Suitable encapsulating material includes starches, poly(vinylacetate), urea/formaldehyde condensate based materials.
  • suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1 ,464,616.
  • Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are, preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato.
  • encapsulating materials include N-Lok manufactured by National Starch.
  • the N-Lok encapsulating material consists of a modified maize starch and glucose.
  • the starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
  • Perfumes Most consumers have come to expect scented laundry products and to expect that fabrics which have been laundered also have a pleasing fragrance. It is also desired by consumers for laundered fabrics to maintain the pleasing fragrance over time. Perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, the amount of perfume carryover from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric. Fragrance materials are often very costly and their inefficient use in rinse added fabric softener compositions and ineffective delivery to fabrics from the rinse results in a very high cost to both consumers and fabric softener manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in fabric softener products, especially for improvement in the provision of long-lasting fragrance to the rinsed fabrics. Therefore, industry continues to seek improved alternatives for generating fragrances through economic and effective means.
  • the present invention encompasses a perfume entity comprising more than one chemical components wherein at least one component is a perfume compound, linked to an amino acid sequence comprising a cellulose binding domain.
  • the perfume compound is linked to the CBD, linking region and/or polyreactive linking region via a weak bond. It is believed that high substantivity of the perfume will be achieved by linking perfume compounds to a CBD. A complex of several perfumes with different perfumery notes can be formed. Also encompassed in the present invention are laundry detergent and/or fabric care compositions comprising one or more of these perfume entities.
  • alcohols represent key notes in perfumery.
  • many alcohols are too volatile to remain in a perceptible way on dry fabrics and/or are not sufficiently fabric substantive to deposit on fabric in an optimum way such as in a softening through-the-wash process.
  • the linking of these perfumery alcohols to the CBD, linking region and/or polyreactive linking region can be achieved for instance via an ester bond to a carboxylic group of the polyreactive linking region or to a molecule of succinic acid which is itself linked to an hydroxy group of the polyreactive linking region.
  • a further example are the perfumery aldehydes known to provide a fresh note on fabrics and especially on dry fabrics.
  • perfumery aldehydes do not deposit substantially enough on the fabrics and/or are too volatile.
  • a known solution to the art consists in using a second perfumery material containing an amine group to form a Shift base. Said Shift bases present a higher residuality on the fabrics but do not have fabric substantivity and cause a change in the aldehyde perfume character.
  • Such perfume entities provide high fabric substantivity which results in the reduction of the perfume waste in the wash of fabric care drain and in increased perfume retention on the fabrics, i.e., increased through the wash deposition.
  • these perfume entities provide significant release of the perfume on laundered dry fabrics.
  • the amine groups encompassed within the CBD, linking region and/or polyreactive linking region of the present invention do not have any odour impact nor change the perfume character.
  • these perfume entities will be comprised at a level of 0% to 10%, preferably 0% to 3%, more preferably 0% to 1% by weight of the total composition.
  • Fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin.
  • the range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation.
  • perfume ingredients some are commercial names conventionally known to one skilled in the art, and also includes isomers. Such isomers are also suitable for use in the present invention.
  • a typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in "perfume and Flavor Chemicals", Vol. I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
  • Preferred for the purpose of the present invention are the aldehydes or ketones based products.
  • Natural products such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil;
  • Alcohols such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol;
  • Aldehydes such as citral, HelionalTM, alpha-hexyl-cinnamaldehyde, hydroxycitronellal, LilialTM (p-tert. butyl-alpha -methyldihydrocinnamaldehyde), methylnonylacetaldehyde, 1-decanal, benzaldehyde, fiorhydral, 2,4-dimethyl-3- cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1 -carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, P.T.
  • - Ketones such as allylionone, alpha-ionone, beta -ionone, isoraldein (isomethyl- alpha -ionone), methylionone, Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super, 2,4,4, 7-Tetramethyl- oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof; - Esters such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl etho
  • Acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States Patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-lndanes, see U.S. Pat. No. 5 ,084,440, issued January 28, 1992, assigned to Givaudan Corp. ;
  • Recent synthetic specialties include the enol ethers of alkyl-substituted oxo- tetralins and oxo-indanes as described in U.S. Pat. 5,332,725, July 26, 1994, assigned to Givaudan; or Schiff Bases as described in U.S. Pat. 5,264,615, December 9, 1991 , assigned to Givaudan.
  • Sanitisation includes all positive effects obtained by the inhibition or reduction of microbial activity on fabrics and other surfaces, such as the prevention of malodour development and bacterial/fungal growth. For example, it provides prevention of malodour development on stored and weared fabrics.
  • the composition of the invention will inhibit or at least reduce the bacterial and/or fungal development on moist fabric waiting for further laundry processing and thereby preventing the formation of malodour.
  • the term hygiene agents herein encompasses fungicides and antimicrobials that when applied to fabric respectively prevent or reduce the growth of fungi or bacteria.
  • the sanitisation benefits of the laundry detergent and/or fabric care compositions of the present invention can be evaluated by the Minimum Inhibitory Concentration (MIC) as described in Tuber. Lung. Dis. 1994 Aug; 75(4):286-90; J. Clin. Microbiol. 1994 May; 32(5):1261-7 and J. Clin. Microbiol. 1992 Oct; 30(10):2692-7.
  • MIC Minimum Inhibitory Concentration
  • the present invention encompasses an hygiene agent entity.
  • This hygiene agent entity comprises more than one chemical components wherein at least one component is a hygiene agent, linked to an amino acid sequence comprising a Cellulose Binding Domain.
  • the hygiene agent will be linked to the CBD, linking region and/or polyreactive linking region via weak bond in order to release the active material upon time during or after the wash or fabric care process.
  • Such hygiene agent entity can be incorporated in a laundry detergent and/or fabric care composition of the present invention.
  • the hygiene agent comprises an hydroxyl, carboxyl or aldehyde reactive moiety. It has been surprisingly found that such hygiene agent entities provide long lasting and efficient control of the micro-organism growth on stored and weared fabrics.
  • Preferred antibacterial compounds are pentadecanol, cinamaldehyde, ionone, glutaraldehyde, citronellal.
  • Other suitable antimicrobial compounds with an hydroxyl, carboxyl or aldehyde moiety are described in perfumes Cosmetiques
  • Nerodol which can for example be linked to the carboxylic groups or succinic acid linked to the alcohol group of the CBD, linking region and/or polyreactive linking region.
  • a further example are the compounds Cipamaldehyde and/or Beta ionone which can form for example a Shift base or ⁇ -amino ketone with the NH2 groups of the CBD, linking region and/or polyreactive linking region.
  • microbicidally active ingredients described in the handbook of Disinfectants and Antiseptics edited by J.M. Ascenzi and in WO97/46218 such as 2-hydroxydiphenyl ether, phenol derivatives, diphenyl compounds, benzyl alcohols, chlorhexidine, C12-14 alkylbetaines and C8-18 fatty acid amido alkylbetaines, amphoteric surfactants, trihalocarbanilides and quaternary ammonium salts.
  • cationic germicides described in EP 843 002 and in WO98/24314 and the antibacterial agents triclosan, triclocarban, DMDM hydantoin, piroctone olamine, zinc pyrithione, selenium disulfide, climnazole and 3-methyl-4-(1-methylethyl)phenol also therein described.
  • suitable fungicides are given in WO94/10286 (Henkel), CA943 429 (Unilever) and US3,426,024 (Henkel).
  • Preferred antimicrobials are 2- thiocyanomethylthiobenzothiazole (Busan 30 WB ex Buckmann), butyl 4- hydroxybenzoate (Butyl Parabens ex Nipa Labs), propyl 4-hydroxybenzoate (Propyl Parabens ex Nipa Labs), Terpineol, Borneol, Fenchyl alcohol, trichlorocarbanilidem, Irgasan DP300 (2,4,4'-trichloro 2'hydroxydiphenylehter) and the higher homologues of hydroxybenzoate esters.
  • bactericides used in the hygiene agent entities of this invention include formaldehyde, 2-bromo-2-nitro-propane-1 ,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline- 3-one sold by Rohm and Haas Company under the trade name Kathon.
  • agents illustrated in this compilation 1- or 2-hexadecanol, 2-tetradecanol, 1-pentadecanol, 1-Undecanol, 2-dodecanol, 1-Tridecanol, nerolidiol, hinokitiol, tropolone, berberine, citronellic acid, Curcumin, 2- Mercaptopyridine N-oxide, Ellagic acid (dihydrate), 3-t-Butyl-5-methyl salicylic acid, 3-, 4- or 5-methyl salicylic acid, 1-nonanol, Decylalcohol, Cinamaldehyde, S- or R-Citronellal, Citronellol, Beta-ionone, Thujone, Coumarin and derivatives, Geraniol, Citral, Thymol, Iso-butyl- or Isopropyl-quinoline, 2-butyl-5-methylphenol, 2-Mercapto-3-pyrodinol, Perillyl alcohol, 6-hydroxy-1
  • the levels of hygiene agent entity should be such that they prevent bacterial and fungi growth on fabrics, rather than merely preventing growth within the laundry detergent and/or fabric care compositions per se.
  • this hygiene agent entity will be comprised at a level of 0% to 10%, preferably 0.00001% to 5%, more preferably 0.01 % to 1% by weight of the total composition.
  • the present invention encompasses insect control agent entities.
  • This insect control agent entity comprises more than one chemical components wherein at least one component is an insect control agent, linked to an amino acid sequence comprising a Cellulose Binding Domain.
  • Laundry detergent and/or fabric care compositions of the present invention can comprise such insect control agent entity. It has been surprisingly found that such insect control agent entities provide long lasting insect control by the slow release of the insect control agent.
  • Such insect control agents are linked to the CBD, linking region and/or polyreactive linking region preferably via a weak bond in order to release upon time the active material.
  • these materials can be linked to the NH2 group present in the CBD, linking region and/or polyamino polymer via a Shift base or Michael reaction.
  • insect control agent refers to both insecticides and insect repellents either individually or as mixtures.
  • Suitable insect repellents include aldehyde based compounds such as Citronellal and Rotundial, ene one based compounds such as Butopyronoxyl (Indalone TM), benzyl benzoate, bioallethrin and dimethrin, N,N- diethyl toluamide (“DEET”), N,N-diethyl benzamide, p-menthane-3,8-diol, 1S,3S,4S,6S-carene-3,4diol (Sumitomo - US5,130,136), 1-piperidinecarboxylic acid, 2-(2-hydroxyethyl)-, 1-methylpropylester, 1-(3cyclohexen-1-yl carbonyl)- 2methylpiper
  • WO98/17772 describes the insect repellent agent 3-(N- butylacetamino) ethyl propionate for use in detergents.
  • Preferred insect repellents are aldehyde based compounds such as Citronellal and Rotundial.
  • insect control agent entities are generally comprised in the laundry detergent and/or fabric care compositions of the present invention at a level of from 0.1% to 20%, preferably 0.1% to 10%, more preferably 0.1% to 6% by weight of the composition.
  • the present invention encompasses a bleaching entity comprising more than one chemical components wherein at least one component is a bleaching agent, linked to an amino acid sequence comprising a cellulose binding domain.
  • Said bleaching agent can be selected from hydrophilic bleach activator, hydrophobic bleach activator, metal catalyst and/or photoactivated bleach. It has been surprisingly found that the bleaching action with such bleaching entities results in improved stain/soil bleaching/removal and whiteness maintenance.
  • laundry detergent and/or fabric care compositions comprising such a bleaching entity.
  • the bleach activator is linked to the CBD via a linking region, more preferably via a polyreactive linking region.
  • a linking region more preferably via a polyreactive linking region.
  • Hydrophilic bleach activator For example, Tetra Acetyl Ethylene Diamine (TAED) is a current bleach activator used in laundry detergent and forms peracetic acid in presence of H2O2. It is known that the two NH2 groups of the Ethylene Diamine are diacetylated to form TAED. Without wishing to be bound by theory, it is believed that the diacetylation of the free NH2 groups of the CBD, linking region or polyreactive linking region, forms a substantive fabric hydrophilic bleach activator. Hydrophilic bleach activator of the TAED type can be linked for example via a diacetylation reaction to any NH2 groups of the CBD, linking region and/or polyreactive linking region of the present invention.
  • TAED Tetra Acetyl Ethylene Diamine
  • Hydrophobic bleach activators such as Nonanoyl benzene sulphonate, are current bleach activators used in laundry detergent. It has been surprisingly found that the phenolic moiety can be replaced by the one present in the tyrosine amino acid present in the CBD, linking region and/or polyreactive linking region. Active hydrophobic bleach activator precursors such as nonanyl unit can be linked to the phenol group of an amino acid such as tyrosine present in the peptidic CBD, linking region and/or polyreactive linking region. Similarly, if there is no phenol entity available in the CBD, linking region and/or polyreactive linking region, a phenol unit can be linked to a group NH2 in this CBD, linking region and/or polyreactive linking region. Hydrophobic bleach activators in general can be linked to the CBD, linking region and/or polyreactive linking region for example by a reaction on NH2 groups.
  • hydrophobic bleach activators are nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG) or Phenolsulfonate ester of N-nonanoyl-6- aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • NOBS nonanoyloxybenzene-sulfonate
  • ISONOBS 3,5,- trimethylhexanoloxybenzenesulfonate
  • PAG pentaacetylglucose
  • NACA-OBS Phenolsulfonate ester of N-nonanoyl-6- aminocaproic acid
  • bleach activators are the activators based on a caprolactam leaving group such as benzoyl caprolactam and quaternary ammonium hexanoyl caprolactam; the imides activators such as N-nonanoyl-N-methyl acetamide and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications US serial No. 60/022,786 (filed July 30, 1996) and No. 60/028,122 (filed October 15, 1996) :
  • Ri is a C7-C13 linear or branched chain saturated or unsaturated alkyl group
  • R2 is a C ⁇ -Cs ] linear or branched chain saturated or unsaturated alkyl group
  • R3 is a C-1-C4 linear or branched chain saturated or unsaturated alkyl group.
  • pre-fromed peracid such as nonylamido peroxy adipic acid and N,N-phtaloylaminoperoxy caproic acid and the Di-acyl peroxides such as dobenzoyl peroxide.
  • Metal catalysts The third type of bleach activator that can be linked to one or more CBD(s) are the below described metal catalysts. For example, these catalysts can be linked via their capping cyclo azo moieties to NH2 groups of the CBD, linking region and/or polyreactive linking region.
  • Metal-containing catalysts for use in bleach compositions include cobalt-containing catalysts such as Pentaamine acetate cobalt(lll) salts and manganese-containing catalysts such as those described in EPA 549 271 ; EPA 549 272; EPA 458 397; US 5,246,621 ; EPA 458 398; US 5,194,416 and US 5,114,611.
  • Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.
  • Photoactivated bleach Another group of suitable bleach activators that can be linked the CBD, linking region and/or polyreactive linking region of the present invention are the photoactivated bleaches.
  • the linking can be achieved between the NH2 groups of and the benzyls groups of these photoactivated bleaches, activated via a preliminary bromination.
  • Suitable photoactivated bleaching agents are the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • these bleaching entity will be comprised at a level of 0% to 20%, preferably 0% to 10%, more preferably 0% to 5% by weight of the total composition.
  • compositions of the present invention can further comprise bleaching species such as hydrogen peroxide, PB1 , PB4 and percarbonate with a particle size of 400-800 microns, typically be present at levels of from about 1% to about 25%.
  • bleaching species such as hydrogen peroxide, PB1 , PB4 and percarbonate with a particle size of 400-800 microns, typically be present at levels of from about 1% to about 25%.
  • the present invention encompasses a fabric softening entity.
  • This fabric softening entity comprises more than one chemical components wherein at least one component is a softening component, linked to an amino acid sequence comprising a cellulose binding domain.
  • These fabric softening entities can be incorporated in a laundry detergent and/or fabric care composition. It has been surprisingly found that such fabric softening entities provide, refurbish or restore tensile strength, anti-wrinkle, anti-bobbling and anti-shrinkage properties to fabrics, as well as provide static control, fabric softness, colour appearance and fabric anti-wear properties and benefits.
  • Durable press garments include those garments which resist wrinkling of the fabric both during wear and during the laundering process.
  • Durable press garments can greatly decrease the hand work associated with laundering by eliminating ironing sometimes necessary to prevent wrinkling of the garment.
  • the fabric's ability to resist wrinkling is reduced over time as the garment is repeatedly worn and laundered.
  • these fabric softening entities will be comprised at a level of 0% to 50%, preferably 0% to 30, more preferably 0% to 15% by weight of the total composition.
  • One suitable softening component are dialkyl units that can be linked for example, by dialkylation of the NH2 groups comprised in the CBD, linking region an/or polyreactive linking region.
  • Preferably such fabric softening entities will not comprise a weak bond.
  • Dialkyl units suitable for the compositions of the present invention can be extracted from the following cationic softening surfactants currently used in the laundry detergent and/or fabric care context.
  • the alkyl, or alkenyl chain must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.
  • the chain may be straight or branched.
  • Specific examples of the alkyl or alkenyl chains herein include : 1) N,N-di(tallowyl-oxy-ethyl); 2) N,N-di(2-tallowyloxy-2-oxo-ethyl);
  • alkyl chains for the purpose of the present invention N,N-di(tallowoyl- oxy-ethyl), where the tallow chains are at least partially unsaturated.
  • Suitable softening components include quaternary ammonium softening compounds having a solubility in water at pH2.5 and 20°C of less than 10g/l. It is particularly advantageous if the softening component is a quaternary ammonium compound in which at least one long chain alkyl group is connected to the quaternary ammonium compound via at least one ester link.
  • Suitable cationic softener are described in US4,137,180 (Naik) and WO93/23510.
  • Suitable clays include a three layered smectite clay, preferably having a cationic exchange capacity as described in GB 1 ,400,898 and in USP 5,019,292.
  • any polymeric lubricant suitable for softening a fabric include silicone and in particular those described in GB1 , 549,180, EP 459 821 (Unilever) and EP 459 822 (Unilever).
  • the present invention encompasses a dye fixative entity.
  • This dye fixative entity comprises more than one chemical components wherein at least one component is a dye fixative agent, linked to an amino acid sequence comprising a cellulose binding domain.
  • laundry detergent and/or fabric care compositions comprising a dye fixative entity. It has been surprisingly found that such dye fixative entities provide improved anti-wear properties, colour appearance.
  • coloured garments have a tendency to wear and show appearance losses. A portion of this colour appearance loss may be attributed to abrasion in the laundering process, particularly in automatic washing machines and automatic laundry dryers.
  • Dye fixing agents, or "fixatives” are well-known, commercially available materials which are designed to improve the appearance of dyed fabric by minimising the loss of dye from fabrics due to washing. Many dye fixatives are cationic, and are based on various quaternized or otherwise cationically charged organic nitrogen compounds. Fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981 , Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No.
  • SANDOFIX TPS which is also available from Sandoz and is a preferred polycationic fixative for use herein and SANDOFIX SWE (cationic resinous compound), REWIN SRF, REWIN SRF-O and REWIN DWR from CHT-Beitlich GMBH.
  • Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid - diamine condensates e.g.
  • the amount of dye fixing entities to be employed in the composition of the invention is preferably from about 0.01% to about 15% by weight of the composition, more preferably from about 0.1% to about 15% by weight, most preferably from about 0.25% to about 10% by weight of the composition.
  • the present invention encompasses a soil release entity.
  • This soil release entity comprises more than one chemical components wherein at least component is a soil release material, linked to an amino acid sequence comprising a cellulose binding domain. It has been surprisingly found that such modified soil release material provide better deposition of the soil release agent onto the fabric and therefore better soil release performance.
  • laundry detergent and/or fabric care compositions comprising a soil release entity.
  • the soil release material suitable in the present invention are ethylene glycols oligomers, polyethylene glycol and derivatives such as transesterified polyethylene glycols, and propylene polyoxy ethylene.
  • Other suitable soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula
  • modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end- capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
  • DMT dimethyl terephthalate
  • PG ,2-propylene glycol
  • Gosselink et al for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • the present invention encompasses a brightener entity.
  • This brightener entity comprises more than one chemical components wherein at least one component is a brightener, linked to an amino acid sequence comprising a cellulose binding domain. It has been surprisingly found that such brightener entity provides better deposition of the brightener onto the fabric and therefore better whiteness maintenance performance.
  • various brighteners not currently used in the detergent field could also be used in the present invention thanks to their increased fabric substantivity, in particular during a softening-through-the-wash process. Preferably, such brightener entities will not comprise a weak bond.
  • laundry detergent and/or fabric care compositionscomprising a brightener entity are also encompassed.
  • compositions herein may contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.001% to 3.5% by weight of such optical brighteners.
  • Suitable brighteners for compositions of the present invention are :
  • Stilbenyl-2H-triazoles such as stilbenyl-2H-naphtol[1 ,2-d]triazoles and bis(1 ,2,3-triazol-2-yl)stilbenes,
  • Benzo[b]furnas and Benzimidazoles such as bis(benzo[b]furan-2- yl)biphenyls and cationic benzimidazoles,
  • a brightener of the Coumarin type can be attached to the NH2 group or to an amido group from the CBD, linking region or polyreactive linking region.
  • Suitable brighteners that can be linked to a CBD according to the present invention are the hydrophilic optical brighteners having the structural formula:
  • is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.
  • the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the present invention encompasses an enzyme entity.
  • This enzyme entity comprises more than one chemical components wherein at least one component is an enzyme which provide cleaning performance, fabric care and/or sanitisation benefits, linked to an amino acid sequence comprising a cellulose binding domain.
  • Also encompassed are laundry detergent and/or fabric care compositions comprising an enzyme entity.
  • the laundry detergent and/or fabric care compositions of the present invention when comprising said enzyme entities, provide improved enzymatic benefits, i.e. improved enzymatic stain removal, enhanced enzymatic fabric care and/or improved enzymatic sanitisation benefits.
  • Said enhanced enzymatic benefits are achieved by means of a process wherein the fabric is contacted with an enzyme entitiy which has increased affinity (relative to unmodified enzyme) for binding to a cellulosic fabric or textile.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
  • a preferred combination is a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • the cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit).
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a " 43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
  • suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Enhancers are generally comprised at a level of from 0.1% to 5% by weight of total composition.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4- carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10- methylphenoxazine (described in WO 94/12621) and substitued syringates (C3- C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Enzymatic system may be used as bleaching agents :
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.
  • lipases ex Pseudomonas gladioli.
  • lipases such as M1 Lipase ⁇ ar >d LipomaxR (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra ⁇ (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation.
  • Addition of cutinases to detergent compositions have been described in e.g. WO-A- 88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
  • Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A” herein.
  • Protease C is a variant of an alkaline serine protease from Bacillus in which Lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C.
  • a carbonyl hydrolase variant of the protease described in WO95/10591 having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101 , +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516 200 by Unilever.
  • the proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1 % pure enzyme by weight of the composition.
  • Amylases can be included for removal of carbohydrate-based stains.
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ - Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
  • ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Ban® .Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ - amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk).
  • amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • the amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used.
  • the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the variant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.
  • the isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes (e.g., cogranulates ).
  • Other suitable chemical components are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes (e.g., cogranulates ).
  • Other suitable chemical components are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more
  • Latex are defined as a material suitable for improving the drape of fabric. Suitable materials include a polyvinylacetate homopolymer such as 9802 (Vinamul). Resins prevent the formation of pills on the fabrics. Suitable resins are Knittex BE from Ciba-Geigy or silicas such as Crosanol NS from Crosfiled.
  • the Cellulose Binding Domain (CBD)
  • Cellulose Binding Domain or CBD are intended to indicate an amino acid sequence capable of effecting binding of the cellulase to a cellulosic substrate (e.g. as described in P. Kraulis et al., Determination of the three-dimensional structure of the C terminal domain of cellobiohydrolase I from Trichoderma reesei. A study using nuclear magnetic resonance and hybrid distance geometry-dynamically simulated annealing. Biochemistry 28:7241-7257, 1989). The classification and properties of cellulose binding domains are presented in P. Tomme et al., in the symposium “Enzymatic degradation of insoluble polysaccharides” (ACS Symposium Series 618, edited by J.N. Saddler and M.H. Penner, ACS, 1995).
  • Cellulose-binding (and other carbohydrate-binding) domains are polypeptide amino acid sequences which occur as integral parts of large polypeptides or proteins consisting of two or more polypeptide amino acid sequence regions, especially in hydrolytic enzymes (hydrolases) which typically comprise a catalytic domain containing the active site for substrate hydrolysis and a carbohydrate- binding domain for binding to the carbohydrate substrate in question.
  • hydrolytic enzymes hydrolases
  • Such enzymes can comprise more than one catalytic domain and one, two or three carbohydrate-binding domains, and they may further comprise one or more polypeptide amino acid sequence regions linking the carbohydrate-binding domain(s) with the catalytic domain(s), a region of the latter type usually being denoted a "linker".
  • Cellulose-binding domains have also been found in algae, e.g. in the red alga porphyra purpurea in the form of a non-hydrolytic polysaccharide- binding protein [see P. Tomme et al., Cellulose-binding domains - Classification and Properties in Enzymatic Degradation of Insoluble Carbohydrates , John N. Saddler and Michael H. Penner (Eds.), ACS Symposium Series, No. 618 (1996)].
  • most of the known CBDs derive from cellulases and xylanases.
  • cellulose-binding domain is intended to be understood in the same manner as in the latter reference (P. Tomme et al., op. cit. )
  • the P. Tomme et al. reference classifies more than 120 "cellulose-binding domains" into 10 families (l-X) which may have different functions or roles in connection with the mechanism of substrate binding. However, it is to be anticipated that new family representatives and additional families will appear in the future.
  • a CBD may be located at the N or C terminus or at an internal position.
  • the part of a polypeptide or protein (e.g. hydrolytic enzyme) which constitutes a CBD per se typically consists of more than about 30 and less than about 250 amino acid residues.
  • the molecular weight of an amino acid sequence constituting a CBD per se will typically be in the range of from about 4kD to about 40kD, and usually below about 35kD.
  • Cellulose binding domains can be produced by recombinant techniques as described in H. Stalbrand et al., Applied and Environmental Microbiology, Mar. 1995, pp. 1090-1097; E. Brun et al., (1995) Eur. J. Biochem. 231, pp. 142-148; J.B. Coutinho et al., (1992) Molecular Microbiology 6(9), pp. 1243-1252
  • a cellulose binding domain of, e.g. a cellulase several genetic engineering approaches may be used.
  • One method uses restriction enzyme to remove a portion of the gene and then to fuse the remaining gene-vector fragment in frame to obtain a mutated gene that encodes a protein truncated for a particular gene fragment.
  • Another method involves the use of exonucleases such as Ba131 to systematically delete nucleotides either externally from the 5' and the 3' ends of the DNA or internally from a restricted gap within the gene.
  • exonucleases such as Ba131 to systematically delete nucleotides either externally from the 5' and the 3' ends of the DNA or internally from a restricted gap within the gene.
  • Appropriate substrates for evaluating the binding ability include cellulosic materials such as Avicel TM and cotton fibres.
  • Other methods include the use of a selective or specific protease capable of cleaving a CBD, e.g., a terminal CBD, from the remainder of the polypeptide chain of the protein in question.
  • CBDs for the purpose of the present invention are selected from the group consisting of : CBDs CBHII from Trichoderma reesei, CBD CBHI from Trichoderma reesei and/or CBD family 45 from Humicola insolens. More preferred CBD for the purpose of the present invention is the CBD originating from the fungal Humicola Insolens cellulase sold under the tradename "Carezyme” by Novo Nordisk A/S. Carezyme is an endoglucanase from family 45, derived from Humicola insolens DSM1800, having a molecular weight of about 43kDa and exhibiting cellulolytic activity.
  • Selected Cellulose Binding Domain Selected CBD
  • the present invention also encompasses chemical entities wherein more than one chemical components are linked to a selected cellulose binding domain.
  • Said cellulose binding domain is selected to comprise in its amino acid sequence, at least one Lysine amino acid.
  • the Lysine amino acid(s) and the NH2 of the terminal amino acid will provide suitable attachement points for the chemical components.
  • Suitable cellulose binding domains comprising at least one Lysine amino acid from fungal origin are listed below (Please find into brackets, the gene accession code for the GENBANK database, National Center of Biotechnology Information , NIH): CBD from Humicola insolens endoglucanase (A23644), CBD from the Trichoderma longibrachiatum EGII (X60652) for endo-1 ,4-beta-glucanase, CBD from the plasmid pTT11 for Endo II (A03825 mRNA), CBD from P.
  • CBD bisporus (C54-carb-8) ce13a (Z34007), CBD from Humicola grisea CBHI (X17258), CBD from Humicola xylanase (AB001030), CBD from Fusarium oxysporum C-familiy cellulase (L29379), CBD from Trichoderma reesei (QM9414) endo-1 ,4-beta-glucanase (Z33381), CBD from Agaricus bisporus cellulose-growth-specific protein (M86356), CBD from Neurospora crassa CBH-1 (X77778) and CBD from Porphyra purpurea putative polysaccharide binding domain (U08843).
  • Suitable cellulose binding domains comprising at least one Lysine amino acid from bacterial origin are listed below (Please find into brackets, the gene accession code for the GENBANK database, National Center of Biotechnology Information , NIH):
  • fluoroscens XynB and XynC for xylanase B and arabinofuranosidase C (X54523 or X54523A2)
  • CBD from Mycobacterium tuberculosis cosmid Y39 (Z74025A32)
  • CBD from Thermonospora fusca beta-1 ,4-endoglucanase (L01577)
  • CBD from P. fluoroscens xynD for esterase D X58956)
  • CBD from Cellulomonas fimi (221) ynD (X76729)
  • CBD from A
  • caulinodans EGI Z48958
  • CBD from Fibrobacter succinognes S85 CMC-xylanase U94826
  • CBD from Agrobacterium tumefasciens FlaD F1hB, FliG, FliN, FliM, MotA, FlgF, Flil (U95165 or U95165A22 or U95165A23 or U95165A24), CBD from A.
  • Tumefasciens FlaA, FlaB and FlaC (X96435 or X96435A2 or X96435A3), CBD from Shigella flexneri FliC-SF for flagellin (D16819), CBD from Kurthia zopfii for chitinase (D63702), CBD from Streptomyces halstedii for beta-1 , 4-endoglucanase (ce1A2) (U51222A2), CBD from Mycobacterium tuberculosis cosmid SCY06H11(Z85982A24), CBD from Sinorhizobium meliloti FlgC, FliE, FlgG, FlgA, Flgl and FlgH (L49337A13), CBD from Rhodobacter capsulatus strain SB1003 (AF010496A56), CBD from Streptomyces lividans acetyl-xylan esterase (axeEA) and xylanase
  • thermosulfurigenes pullulanase AmyB maltose binding protein (AmyE) (M57692A2)
  • CBD from Clostridium thermohydrosulfuricum amylopullulanase apu
  • Preferred selected CBDs are selected from the group consisting of : CBDs CenC, CenA and Cex from Cellulomonas fimi, CBD Cellulozome from Clostridium cellulovorans, CBD E3 from Thermonospora fusca, CBD-dimer from Clostridium stecorarium (NCIMB11754) XynA and/or CBD from Bacillus agaradherens (NCIMB40482).
  • the linking region is a peptidic polymer and/or a chemical component is an enzyme
  • a nucleotide sequence encoding the substrate- binding (carbohydrate-binding) region may then be manipulated in a variety of ways to fuse it to a DNA sequence encoding the amino acid sequence of the polyreactive linking region and/or enzyme of interest.
  • the DNA fragment encoding the carbohydrate- binding amino acid sequence, and the DNA encoding the amino acid of the sequence of the polyreactive linking region and/or enzyme of interest are then ligated with or without a linker.
  • the resulting ligated DNA may then be manipulated in a variety of ways to achieve expression.
  • Preferred microbial expression hosts include certain Aspergillus species (e.g. A. niger or A. oryzae), Bacillus species, and organisms such as Escherichia coli or Saccharomyces cerevisiae.
  • the laundry detergent and/or fabric care compositions of the invention must contain at least one additional detergent and/or fabric care component.
  • additional components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • compositions of the invention may for example, be formulated as hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions.
  • Pre-or post treatment of fabric include gel, spray and liquid fabric care compositions.
  • a rinse cycle with or without the presence of softening agents is also contemplated.
  • compositions of the invention When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.
  • the compositions of the invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process. Therein, the levels of the ingredients can be much higher than the conventional levels.
  • the laundry detergent and/or fabric care compositions according to the invention can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular forms.
  • Granular compositions can also be in "compact” form, the liquid compositions can also be in a "concentrated” form. If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at 20°C.
  • compositions herein are best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate.
  • Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
  • the laundry detergent and/or fabric care compositions according to the present invention generally comprise a surfactant system wherein the surfactant can be selected from other nonionic and/or anionic and/or other cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
  • the surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1 % to 35% by weight, most preferably from 1% to 30% by weight of laundry detergent and/or fabric care compositions in accord with the invention.
  • the surfactant is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of c 11-C-15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12- 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodo ⁇ TM 45-9 (the condensation product of C-14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol
  • nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula R2 ⁇ (C n H 2 nO)t(glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PlurafacTM LF404 and PluronicTM surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C ⁇ -C-js alcohol ethoxylates (preferably C10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
  • Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
  • R1 is H, or R 1 is C ⁇
  • R 2 is C5..31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R1 is methyl
  • R 2 is a straight C-j 1-15 alkyl or C-
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: O
  • R is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a Ci-Cg hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R ⁇ is C10- 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R ⁇ is C10- 16 alkyl.
  • alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10- 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10- 20 alkyl component, more preferably a C-12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C10- 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10- 20 alkyl component, more preferably a C-12-C18 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C12- 16 are preferred for lower wash temperatures (e.g. below about 50°C) and C-
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent and/or fabric care compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfa.es containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates containing up to 10 moles of ethylene oxide
  • alkyl glycerol sulfonates fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsatur
  • laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10- 24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12- 20 alkyl or hydroxyalkyl, more preferably C12-
  • A is an ethoxy or propoxy unit
  • m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3
  • M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C-
  • the laundry detergent and/or fabric care compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
  • Cationic detersive surfactants suitable for use in the laundry detergent and/or fabric care compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R3 is selected from the group consisting of -CH2CH2-, -CH 2 CH(CH3)-, -CH 2 CH(CH 2 OH)-, -CH 2 CH2CH 2 -, and mixtures thereof
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH2CHOH-CHOHCOR 6 CHOHCH2OH wherein R ⁇ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
  • R5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R5 is not more than about 18
  • each y is from 0 to about 10 and the sum of the
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
  • y is 2-4, preferably 3. whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,
  • X" is a counterion, preferably a halide, e.g. chloride or methylsulfate.
  • R6 is C ⁇ -C4 and z is 1 or 2.
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R3R4N + X- (i)
  • R1 is C8-C16 alkyl
  • each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4o) x H where x has a value from 2 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for R-j is C12- 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • Suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C-12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R1 is CH2-CH2-O-C-C 12-14 alkyl and R2R3R4 are methyl).
  • the laundry detergent and/or fabric care compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent and/or fabric care compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No.
  • laundry detergent and/or fabric care compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in laundry detergent and/or fabric care compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
  • the laundry detergent and/or fabric care compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R3(OR )XN(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C ⁇ rj- i8 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the laundry detergent and/or fabric care compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the laundry detergent and/or fabric care composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula R1 NH2 wherein R ⁇
  • alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
  • Preferred amines according to the formula herein above are n-alkyl amines.
  • Suitable amines for use herein may be selected from 1-hexylamine, 1- octylamine, 1-decylamine and laurylamine.
  • Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl amido propylamine and amido propylamine.
  • Suitable tertiary amines for use herein include tertiary amines having the formula R1 R2R3N wherein R1 and R2 are C-
  • R3 is either a C6-C12, preferably C ⁇ -C-I Q alkyl chain, or R3 is R4X(CH2)n- whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C12, n is between 1 to 5, preferably 2-3.
  • R5 is H or C1-C2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
  • R ⁇ is C6-C12 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4
  • Most preferred amines of the present invention include 1 -octylamine, 1- hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldi- methylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldimethylamme.
  • the most preferred amines for use in the compositions herein are 1-hexylamine, 1 -octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781 , U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7.
  • bleaching agents including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co- pending applications USSN 08/136,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e., an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e., an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • Suitable technologies which provide a type of colour care benefit can also be included.
  • metallo catalysts for colour maintenance are described in copending European Patent Application No. 92870181.2.
  • Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino-functional polymer for colour care treatment and perfume substantivity are further examples of colour care / fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed November 07, 1996.
  • fabric softening may be inorganic or organic in type.
  • Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292.
  • Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12-C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919.
  • Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A- 0 299 575 and 0 313 146.
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
  • the laundry detergent and/or fabric care compositions according to the present invention may further comprise a builder system.
  • Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopoly- phosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • Phosphate builders can also be used herein.
  • Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
  • Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst).
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na 2 Si 2 O 5 ).
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 ,368, 821 ,369 and 821 ,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfmyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccina.es described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1 ,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelafing agent such as citric acid.
  • Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelafing agent such as citric acid.
  • Preferred builder systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.
  • Other builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1 , 596,756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Detergency builder salts are normally included in amounts of from 5% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.
  • the laundry detergent and/or fabric care compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
  • MGDA water-soluble methyl glycine diacetic acid
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl- alkanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
  • Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxy- ethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the detergent enzymes.
  • Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31 , 1992.
  • Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2 ⁇ ) m (CH2) n CH3 wherein m is 2-3 and n is 6-12. The side- chains are ester-linked to the polyacrylate "backbone” to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
  • the laundry detergent and/or fabric care composition of the present invention can also contain dispersants :
  • Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • compositions of the invention may contain a lime soap peptiser compound, which has preferably a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
  • LSDP lime soap dispersing power
  • the lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.
  • a numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950).
  • This lime soap dispersion test method is widely used by practitioners in this art field being referred to, for example, in the following review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3; W.N. Linfield, Tenside surf, det., volume 27, pages 159-163, (1990); and M.K.
  • Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
  • Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6- aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds.
  • the laundry detergent and/or fabric care compositions according to the present invention can also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents.
  • Said polymeric dye transfer inhibiting agents are normally incorporated into laundry detergent and/or fabric care compositions in order to inhibit the transfer of dyes from coloured fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and po ⁇ yvinylimidazoles or mixtures thereof. Addition of such polymers also enhances the performance of the enzymes according the invention.
  • polyamine N-oxide polymers suitable for use contain units having the following structure formula : P
  • II II II A is NC, CO, C, -O-.-S-, -N- ; x is O or 1;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups.
  • R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000.
  • the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerizafion or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1 :1000000. More preferably from 1 :4 to 1 :1000000, most preferably from 1 :7 to 1 :1000000.
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000, preferably from
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N- vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from
  • the N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
  • the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
  • the laundry detergent and/or fabric care compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
  • Polyvinyloxazolidone The laundry detergent and/or fabric care compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • the laundry detergent and/or fabric care compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average of about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure.
  • the cross- linked polymers entrap the dyes by swelling.
  • compositions of the invention may be used in essentially any washing, cleaning and/or fabric care methods, including soaking methods, pre-treatment methods, methods with rinsing steps for which a separate rinse aid composition may be added and post-treatment methods.
  • the process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder.
  • the process of the invention is conveniently carried out in the course of the cleaning / fabric care process.
  • the method of cleaning / fabric care is preferably carried out at 5°C to 95°C, especially between 10°C and 60°C.
  • the pH of the treatment solution is preferably from 7 to 12.
  • compositions of the present invention are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.
  • the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions.
  • the abbreviated component identifications therein have the following meanings:
  • DTDMAMS Ditalllow dimethyl ammonium methylsulfate. SDASA 1:2 ratio of stearyldimethyl amine:triple-pressed stearic acid.
  • Nai2(A1O2SiO2)i2- 2 7H2 ⁇ having a primary particle size in the range from 0.1 to 10 micrometers (Weight expressed on an anhydrous basis).
  • Citric Anhydrous citric acid Citric Anhydrous citric acid.
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 and 900 micrometres.
  • Bicarbonate Anhydrous sodium hydrogen carbonate with a particle size distribution between 400 and 1200 micrometres.
  • MA/AA 1 Random copolymer of 6:4 acrylate/maleate, average molecular weight about 10,000.
  • TAED Tetraacetylethylenediamine.
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate.
  • Nordisk A/S with polytyrosine and (6-nonamidocaproyl) oxybenzene sulfonate molecules are examples of Nordisk A/S with polytyrosine and (6-nonamidocaproyl) oxybenzene sulfonate molecules.
  • DTPA Diethylene triamine pentaacetic acid.
  • DETPMP Diethyltriamine penta (methylene) phosphonate marketed by Monsanto under the Trade name Dequest
  • Photoactivated Sulfonated alumino phtalocyanine encapsulated in Bleach 1 dextrin soluble polymer Protease Proteolytic enzyme sold under the tradename Savinase,
  • Lipase Lipolytic enzyme sold under the tradename Lipolase
  • PVNO Polyvinylpyridine-N-Oxide with an average molecular weight of 50,000.
  • PVPVI Copolymer of vinylimidazole and vinylpyrrolidone with an average molecular weight of 20,000.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl) stilbene-2:2'-disulfonate.
  • Opacifier Water based monostyrene latex mixture, sold by BASF
  • SRP 1 Anionically end capped poly esters.
  • SRP 2 Diethoxylated poly (1 ,2 propylene terephtalate) short block polymer.
  • HMWPEO High molecular weight polyethylene oxide.
  • PEGx Polyethylene glycol of a molecular weight of x .
  • PEO Polyethylene oxide with an average molecular weight of
  • CBD-Rotundial Reaction product of CBD Cellulozome from Clostridium cellulovorans which is sold under the tradename
  • CBD-Damascone Reaction product of CBD Cellulozome from Clostridium cellulovorans which is sold under the tradename
  • this example illustrates the coupling of a perfume citral, hygiene agent glutaraldehyde or insect control agent citronellal to a CBD.
  • the reaction at equal mol takes place in mild conditions (pH 6 to 9.5, from 1 to 48hours / See for example Wirth, P at al 1991 Biorg.Chem 19, 133, 1991 and Chamow SM et al Bioconjugate chem, 4, 133 1994).
  • the chemicals such as perfume (citral), insect control agent (citronellal) and hygiene agent (glutaraldehyde) are linked to NH2 groups of the CBD, linking region and/or polyreactive linking region via Schiffs base reaction.
  • the reaction could also be completed in anhydrous ethanol that contain a drying agent such as Sodium Sulphate.
  • the reaction is identical with the appropriate number of chemicals per CBD. For example 10 equivalent of aldehyde will be added per mol of CBD from familly III that contain more than 10 Lysines.
  • the CBD having at least one Lysine has a NH2 reactive moiety to be linked to perfume.
  • the CBD is non volatile and does not change the character of the aldehyde.
  • Brightener 1 0.09 0.09 0.09 - 0.09 0.09
  • Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
  • Brightener 2 0.3 0.2 0.3 - 0.1 0.3
  • Brightener 1 0.2 0.2 0.2 0.2 0.2
  • Zeolite A 15.0 15.0 15.0
  • Photoactivated bleach 30 ppm 20 ppm - 10 ppm
  • liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight) :
  • Brightener 1 0.2 0.07 0.1 - -
  • liquid detergent formulations were prepared according to the present invention (Levels are given in parts per weight) :

Abstract

Cette invention concerne une entité chimique comprenant plus d'un composants chimiques qui sont liés à un domaine de liaison de la cellulose. Cette invention concerne également une composition de détergent pour lessive et/ou pour le soin des tissus qui comprend une ou plusieurs de ces entités chimiques. Cette composition de détergent pour lessive et/ou pour le soin des tissus, lorsqu'elle comprend ces entités chimiques, offre une meilleure concentration efficace du composant chimique à la surface du tissu et, donc, de meilleurs résultats.
PCT/US1998/020491 1998-09-30 1998-09-30 Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose WO2000018897A1 (fr)

Priority Applications (35)

Application Number Priority Date Filing Date Title
EP98949649A EP1119613A1 (fr) 1998-09-30 1998-09-30 Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose
MXPA01003381 MXPA01003381A (es) 1998-09-30 1998-09-30 Composiciones detergentes para lavanderia y/o para el cuidado de telas que comprenden componentes quimicos enlazados a un dominio de union a celul
BR9816038-9A BR9816038A (pt) 1998-09-30 1998-09-30 Composições detergentes para a lavagem de roupas e/ou para o cuidado do tecido compreendendo componentes quìmicos ligados a um domìnio para a ligação à celulose
CA002343267A CA2343267A1 (fr) 1998-09-30 1998-09-30 Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose
PCT/US1998/020491 WO2000018897A1 (fr) 1998-09-30 1998-09-30 Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose
AU95930/98A AU9593098A (en) 1998-09-30 1998-09-30 Laundry detergent and/or fabric care compositions comprising chemical componentslinked to a cellulose binding domain
JP2000572344A JP2002525423A (ja) 1998-09-30 1998-09-30 セルロース結合ドメインに連結された化学成分を含む洗濯洗剤および／または布帛ケア組成物
CN98814341A CN1327478A (zh) 1998-09-30 1998-09-30 洗衣洗涤剂和/或织物护理组合物
AU40823/99A AU4082399A (en) 1998-09-30 1999-05-17 Laundry detergent and/or fabric care compositions comprising chemical componentslinked to a cellulose binding domain
CN99813903A CN1329659A (zh) 1998-09-30 1999-05-17 洗衣用洗涤剂和/或织物护理组合物
BR9914182-5A BR9914182A (pt) 1998-09-30 1999-05-17 Composições detergentes de lavanderia e/ou de cuidado de tecidos contendo uma entidade quìmica que contém um auxiliar de deposição com uma alta afinidade com a celulose, um tensoativo e uma protease
ES99923145T ES2263273T3 (es) 1998-09-30 1999-05-17 Composiciones detergentes de tejidos y7o para el cuidado de tejidos que comprenden una entidad quimica que contiene un adyuvante de deposicion con elevada afinidad por la celulosa, un tensioactivo y una proteasa.
EP99923146A EP1117757A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un auxiliaire de depot, et un polymere
CA002342588A CA2342588A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un adjuvant de depot ayant une forte affinite pour la cellulose, un tensioactif et une protease
CA002342586A CA2342586A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un auxiliaire de depot, et un polymere
CA002342530A CA2342530A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant des composants chimiques lies a un domaine de fixation de la cellulose
AU39982/99A AU3998299A (en) 1998-09-30 1999-05-17 Laundry detergent and/or fabric care compositions comprising a chemical entity, which contains a deposition aid, and polymer
PCT/US1999/010854 WO2000018865A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un auxiliaire de depot, et un polymere
DE69930858T DE69930858T2 (de) 1998-09-30 1999-05-17 Waschmittel und/oder gewebebehandlungszusammensetzungen enthaltend eine chemische einheit, die ein absetzungshilfsmittel mit hoher celluloseaffinität enthält, sowie ein tensid und protease
AT99923145T ATE323146T1 (de) 1998-09-30 1999-05-17 Waschmittel und/oder gewebebehandlungszusammensetzungen enthaltend eine chemische einheit, die ein absetzungshilfsmittel mit hoher celluloseaffinität enthält, sowie ein tensid und protease
BR9914110-8A BR9914110A (pt) 1998-09-30 1999-05-17 Composições detergente de lavanderia e/ou de cuidado de tecido compreendendo uma entidade quìmica, que contém um auxiliar de deposição e um polìmero
AU39981/99A AU3998199A (en) 1998-09-30 1999-05-17 Laundry detergent and/or fabric care compositions comprising a chemical entity which contains a deposition aid with high affinity for cellulose, a surfactant and a protease
CN99813900A CN1329658A (zh) 1998-09-30 1999-05-17 洗衣用洗涤剂和/或织物护理组合物
PCT/US1999/010853 WO2000018864A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un adjuvant de depot ayant une forte affinite pour la cellulose, un tensioactif et une protease
CN99813904A CN1329666A (zh) 1998-09-30 1999-05-17 洗衣洗涤剂和/或织物护理组合物
PCT/US1999/010855 WO2000018898A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant des composants chimiques lies a un domaine de fixation de la cellulose
EP99924286A EP1117770A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant des composants chimiques lies a un domaine de fixation de la cellulose
JP2000572313A JP2003521558A (ja) 1998-09-30 1999-05-17 付着補助体を含む化学的存在物、およびポリマーを含有した洗濯洗剤および／または布帛ケア組成物
EP99923145A EP1115828B1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un adjuvant de depot ayant une forte affinite pour la cellulose, un tensioactif et une protease
JP2000572312A JP2003526699A (ja) 1998-09-30 1999-05-17 セルロースに高親和性を有する付着補助体を含む化学的存在物、界面活性剤およびプロテアーゼを含有した洗濯洗剤および／または布帛ケア組成物
JP2000572345A JP2003521559A (ja) 1998-09-30 1999-05-17 セルロース結合ドメインに連結された化学成分を含む洗濯洗剤および／または布帛ケア組成物
ARP990104943A AR020543A1 (es) 1998-09-30 1999-09-30 Composiciones con accion detergente para el lavado de ropa y/o con aplicacion para el cuidado de las telas que comprenden una entidad quimica y metodosempleados en el uso.
ARP990104946A AR020546A1 (es) 1998-09-30 1999-09-30 Composiciones con accion detergente para el lavado de ropa y/o con aplicacion para el cuidado de las telas que comprenden una entidad quimica mejorada.
ARP990104944A AR020544A1 (es) 1998-09-30 1999-09-30 Composicion con accion detergente para el lavado de ropa y/o con aplicaciones de cuidado de la tela que comprenden una entidad quimica, un agentetensoactivo y una proteasa.
ARP990104945A AR020545A1 (es) 1998-09-30 1999-09-30 Composiciones con accion detergente para el lavado de ropa y/o con aplicacion para el cuidado de las telas que comprenden una entidad quimica y un polimero.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/020491 WO2000018897A1 (fr) 1998-09-30 1998-09-30 Compositions de detergents pour lessive et/ou pour le soin des tissus comprenant des composants chimiques lies a un domaine de liaison de la cellulose

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PCT/US1999/010855 WO2000018898A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant des composants chimiques lies a un domaine de fixation de la cellulose
PCT/US1999/010853 WO2000018864A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un adjuvant de depot ayant une forte affinite pour la cellulose, un tensioactif et une protease
PCT/US1999/010854 WO2000018865A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un auxiliaire de depot, et un polymere

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PCT/US1999/010853 WO2000018864A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un adjuvant de depot ayant une forte affinite pour la cellulose, un tensioactif et une protease
PCT/US1999/010854 WO2000018865A1 (fr) 1998-09-30 1999-05-17 Compositions de detergents a lessive et/ou de soin des tissus, comprenant une entite chimique qui contient un auxiliaire de depot, et un polymere

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AU4082399A (en) 2000-04-17
BR9914182A (pt) 2001-06-19
ES2263273T3 (es) 2006-12-01
EP1117757A1 (fr) 2001-07-25
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JP2003526699A (ja) 2003-09-09
AU3998199A (en) 2000-04-17
CN1327478A (zh) 2001-12-19
AR020546A1 (es) 2002-05-15
BR9816038A (pt) 2001-10-23
JP2003521559A (ja) 2003-07-15
EP1119613A1 (fr) 2001-08-01
WO2000018898A1 (fr) 2000-04-06
MXPA01003381A (es) 2001-10-01
EP1117770A1 (fr) 2001-07-25
CN1329658A (zh) 2002-01-02
AR020544A1 (es) 2002-05-15
BR9914110A (pt) 2001-06-12
WO2000018864A1 (fr) 2000-04-06
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CN1329666A (zh) 2002-01-02
AR020543A1 (es) 2002-05-15
CA2342588A1 (fr) 2000-04-06
JP2002525423A (ja) 2002-08-13
EP1115828A1 (fr) 2001-07-18
CN1329659A (zh) 2002-01-02
WO2000018865A1 (fr) 2000-04-06
ATE323146T1 (de) 2006-04-15
DE69930858D1 (de) 2006-05-24
AR020545A1 (es) 2002-05-15
AU3998299A (en) 2000-04-17
CA2342586A1 (fr) 2000-04-06
DE69930858T2 (de) 2006-11-30
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JP2003521558A (ja) 2003-07-15
AU9593098A (en) 2000-04-17

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